Trace element fractionation and transport in boreal rivers and soil porewaters of permafrost-dominated basaltic terrain in Central Siberia

The chemical status of ∼40 major and trace elements (TE) and organic carbon (OC) in pristine boreal rivers draining the basaltic plateau of Central Siberia (Putorana) and interstitial solutions of permafrost soils was investigated. Water samples were filtered in the field through progressively decreasing pore size (5 μm → 0.22 μm → 0.025 μm → 10 kDa → 1 kDa) using cascade frontal filtration technique. Most rivers and soil porewaters exhibit 2-5 times higher than the world average concentration of dissolved (i.e., <0.22 μm) iron (0.03-0.4 mg/L), aluminum (0.03-0.4 mg/L), OC (10-20 mg/L) and various trace elements that are usually considered as immobile in weathering processes (Ti, Zr, Ga, Y, REEs). Ultrafiltration revealed strong relationships between concentration of TE and that of colloidal Fe and Al. According to their partition during filtration and association with colloids, two groups of elements can be distinguished: (i) those weakly dependent on ultrafiltration and that are likely to be present as truly dissolved inorganic species (Li, Na, K, Si, Mn, Mo, Rb, Cs, As, Sb) or, partially (20-30%) associated with small size Fe- and Al-colloids (Ca, Mg, Sr, Ba) and to small (<1-10 kDa) organic complexes (Co, Ni, Cu, Zn), and (ii) elements strongly associated with colloidal iron and aluminum in all ultrafiltrates largely present in 1-100 kDa fraction (Ga, Y, REEs, Pb, V, Cr, Ti, Ge, Zr, Th, U). TE concentrations and partition coefficients did not show any detectable variations between different colloidal fractions for soil porewaters, suprapermafrost flow and surface streams. TE concentration measurements in river suspended particles demonstrated significant contribution (i.e., ?30%) of conventionally dissolved (<0.22 μm) forms for usually “immobile” elements such as divalent transition metals, Cd, Pb, V, Sn, Y, REEs, Zr, Hf, Th. The Al-normalized accumulation coefficients of TE in vegetation litter compared to basalts achieve 10-100 for B, Mn, Zn, As, Sr, Sn, Sb, and the larch litter degradation is able to provide the major contribution to the annual dissolved flux of most trace elements. It is hypothesized that the decomposition of plant litter in the topsoil horizon leads to Fe(III)-, Al-organic colloids formation and serves as an important source of elements in downward percolating fluids.     

New operational method of testing colloid complexation with metals in natural waters

A dialysis procedure was used to assess the distribution coefficients of ∼50 major and trace elements (TEs) between colloidal (1 kDa–0.22 μm) and truly dissolved (<1 kDa) phases in Fe- and organic-rich boreal surface waters. These measurements allowed quantification of both TE partitioning coefficients and the proportion of colloidal forms as a function of solution pH (from 3 to 8). Two groups of elements can be distinguished according to their behaviour during dialysis: (i) elements which are strongly associated with colloids and exhibit significant increases of relative proportion of colloidal forms with pH increase (Al, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hf, Mn, Ni, Pb, rare earth elements (REEs), Sr, Th, U, Y, Zn, Zr and dissolved organic C) and (ii) elements that are weakly associated with colloids and whose distribution coefficients between colloidal and truly dissolved phases are not significantly affected by solution pH (As, B, Ca, Cs, Ge, K, Li, Mg, Mo, Na, Nb, Rb, Sb, Si, Sn, Ti, V). Element speciation was assessed using the Visual MINTEQ computer code with an implemented NICA-Donnan humic ion binding model and database. The model reproduces quantitatively the pH-dependence of colloidal form proportion for alkaline-earth (Ba, Ca, Mg, Sr) and most divalent metals (Co, Cd, Mn, Ni, Pb, Zn) implying that the complexation of these metals with low molecular weight organic matter (<1 kDa fraction) is negligible. In contrast, model prediction of colloidal proportion (fraction of 1 kDa–0.22 μm) of Cu²⁺ and all trivalent and tetravalent metals is much higher than that measured in the experiment. This difference may be explained by (i) the presence of strong metal-binding organic ligands in the <1 kDa fraction whose stability constants are several orders of magnitude higher than those of colloidal humic and fulvic acids and/or (ii) coprecipitation of TE with Fe(Al) oxy(hydr)oxides in the colloidal fraction, whose dissolution and aggregation controls the pH-dependent pattern of TE partitioning. Quantitative modeling of metal – organic ligand complexation and empirical distribution coefficients corroborate the existence of two colloidal pools, formerly reported in boreal surface waters: “classic” fulvic or humic acids binding divalent transition metals and alkaline-earth elements and large-size organo-ferric colloids transporting insoluble trivalent and tetravalent elements.     

Control of organic and iron colloids on arsenic partition and transport in high arsenic groundwaters in the Hetao basin, Inner Mongolia

Due to the importance of colloids in regulating element transport and mobility in aquifers, As distribution in the colloidal fraction needs to be identified in high As groundwaters. Groundwater samples were filtered in the field through a progressively decreasing pore size (0.45 μm, 100, 30, 10, 5 kDa) using a filtration technique under a N₂ atmosphere. Major and trace elements and organic C (OC) were measured in (ultra)filtrates. The studied groundwater samples have typical physio-chemical characteristics of the basin waters. Declines in concentrations of alkali (Na, K), alkaline-earth (Mg, Ca, Sr, Ba) elements, Mo, Si and Se during ultrafiltration are smaller relative to other elements. Arsenic, Cu, Cr, U and V are generally about 30% lower in 5 kDa ultrafiltrates in comparison with 0.45 μm filtrates. Around 50% of Fe, OC and Al are bound to colloids with grain size between 5 kDa and 0.45 μm. Two types of colloids, including large-size Fe colloids and small-size organic colloids, have been identified. Results indicate that As would be more likely to be associated with small-size organic colloids than Fe colloids. SEM images and EDS analysis and synchrotron XRF analyses confirm the association of As with NOM with molecular weights of 5-10 kDa. The better correlation between As(V) and OC in the 5-10 kDa fraction indicates that the small-size organic colloids have a greater affinity for As(V) than As(III). Arsenic associated with organic complexes may not be immobilized by adsorption, and, therefore, easily transported in the aquifer. Thus, the presence of As-containing colloidal complexes in high As groundwaters must be considered in the modeling of As transport in the aquifers.     

Interactions between dissolved organic carbon and mercury species in surface waters of the Florida Everglades

An ultrafiltration procedure has been developed to study the interaction between organic C and Hg species in natural waters, and a pilot study was conducted in the surface waters of the Florida Everglades. Compared to total Hg, CH₃Hg shows different distribution patterns in the suspended particulate, colloidal, and truly dissolved phases. Colloidal forms (0.22 μm, 3 kDa) contain the majority of the total dissolved Hg, while the amount found in the truly dissolved fraction (<3 kDa) is small (about 10%). However, CH₃Hg, which shows strong binding capability with low molecular-weight dissolved organic C, is present almost entirely in the lower molecular-weight fraction of the colloids and in the truly dissolved fraction. Quantitative CH₃Hg data correlate well with those for dissolved organic C, an indication that the organic matter present in the system plays an important role in the fate and transport of organomercury. Distribution coefficients between water and the different-sized fractions of the dissolved organic C were determined for both total Hg and CH₃Hg. Results for total Hg were in general agreement with other reports resulting from studies of molecular size distributions of total Hg in freshwater systems. This is, to the best of our knowledge, the first report of such distribution profiles for CH₃Hg between different-sized fractions of dissolved organic C in natural waters.     

Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

Lanthanoid behaviour in an acidic landscape

Lanthanoids were studied in a boreal landscape where an abundance of acid sulfate soils and Histosols provide a unique opportunity to increase the understanding of how these metals behave in acidic soils and waters and interact with soil and aqueous organic matter. In the acid sulfate soils lanthanoids are mobile as reflected in high to very high concentrations in soil water and runoff (typically a few mg l⁻¹ but up to 12 mg l⁻¹) and abundant release by several relatively weak extractants (ammonium acetate EDTA, sodium pyrophosphate, hydroxylamine hydrochloride) applied on bulk soil. Normalisation with the lanthanoid pool in the underlying parent materials (sulphide-bearing sediments deposited in brackish-water) and soil water showed that the extensive release/retention in the acidic soil was accompanied by large, and variable, fractionation trends across the lanthanoid series. In low-order streams draining these soils, the lanthanoid concentrations were high and, as indicated by frontal ultrafiltration and geochemical modelling, largely dissolved (<1 kDa) in the form of the species LnSO₄⁺ and Ln³⁺. In other moderately acidic stream waters (pH 4.3-4.6), organic complexation was predicted to be important in the <1 kDa fraction (especially for the heavy lanthanoids) and strongly dominating in the colloidal phase (1 kDa-0.45 μm). Along the main stem of a stream in focus (catchment area of 223 km²), lanthanoid concentrations increased downstream, in particular during high flows, caused by a downstream increase in the proportion of acid sulfate soils which are extensively flushed during wet periods. The geochemical models applied to the colloidal Ln-organic phase were not successful in predicting the measured fractionation patterns.     

Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia)

The chemical status of major and trace elements (TE) in various boreal small rivers and watershed has been investigated along a 1500-km transect of NW Russia. Samples were filtered in the field through a progressively decreasing pore size (5, 0.8 and 0.22 μm; 100, 10, and 1 kD) using a frontal filtration technique. All major and trace elements and organic carbon (OC) were measured in filtrates and ultrafiltrates. Most rivers exhibit high concentration of dissolved iron (0.2–4 mg/l), OC (10–30 mg/l) and significant amounts of trace elements usually considered as immobile in weathering processes (Ti, Zr, Th, Al, Ga, Y, REE, V, Pb). In (ultra)filtrates, Fe and OC are poorly correlated: iron concentration gradually decreases upon filtration from 5 μm to 1 kD whereas the major part of OC is concentrated in the <1–10 kD fraction. This reveals the presence of two pools of colloids composed of organic-rich and Fe-rich particles. According to their behavior during filtration and association with these two types of colloids, three groups of elements can be distinguished: (i) species that are not affected by ultrafiltration and are present in the form of true dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, Si, B, As, Sb, Mo) or weak organic complexes (Ca, Mg, Sr, Ba), (ii) elements present in the fraction smaller than 1–10 kD prone to form inorganic or organic complexes (Mn, Co, Ni, Zn, Cu, Cd, and, for some rivers, Pb, Cr, Y, HREE, U), and (iii) elements strongly associated with colloidal iron in all ultrafiltrates (P, Al, Ga, REE, Pb, V, Cr, W, Ti, Ge, Zr, Th, U). Based on size fractionation results and taking into account the nominal pore size for membranes, an estimation of the effective surface area of Fe colloids was performed. Although the total amount of available surface sites on iron colloids (i.e., 1–10 μM) is enough to accommodate the nanomolar concentrations of dissolved trace elements, very poor correlation between TE and surface sites concentrations was observed in filtrates and ultrafiltrates. This strongly suggests a preferential transport of TE as coprecipitates with iron oxy(hydr)oxides. These colloids can be formed on redox boundaries by precipitation of Fe(III) from inflowing Fe(II)/TE-rich anoxic ground waters when they meet well-oxygenated surface waters. Dissolved organic matter stabilizes these colloids and prevents their aggregation and coagulation. Estuarine behavior of several trace elements was studied for two small iron- and organic-rich rivers. While Si, Sr, Ba, Rb, and Cs show a clear conservative behavior during mixing of freshwaters with the White sea, Al, Pb and REE are scavenged with iron during coagulation of Fe hydroxide colloids.     

Iron and manganese diagenesis in deep sea volcanogenic sediments and the origins of pore water colloids

Volcanogenic sediments are typically rich in Fe and Mn-bearing minerals that undergo substantial alteration during early marine diagenesis, however their impact on the global biogeochemical cycling of Fe and Mn has not been widely addressed. This study compares the near surface (0-20 cm below sea floor [cmbsf]) aqueous (<0.02 μm) and aqueous + colloidal here in after ‘dissolved’ (<0.2 μm) pore water Fe and Mn distributions, and ancillary O_2(aq), and solid-phase reactive Fe distributions, between two volcanogenic sediment settings: [1] a deep sea tephra-rich deposit neighbouring the volcanically active island of Montserrat and [2] mixed biosiliceous-volcanogenic sediments from abyssal depths near the volcanically inactive Crozet Islands archipelago. Shallow penetration of O_2(aq) into Montserrat sediments was observed (<1 cmbsf), and inferred to partially reflect oxidation of fine grained Fe(II) minerals, whereas penetration of O_2(aq) into abyssal Crozet sediments was >5 cmbsf and largely controlled by the oxidation of organic matter. Dissolved Fe and Mn distributions in Montserrat pore waters were lowest in the surface oxic-layer (0.3 μM Fe; 32 μM Mn), with maxima (20 μM Fe; 200 μM Mn) in the upper 1-15 cmbsf. Unlike Montserrat, Fe and Mn in Crozet pore waters were ubiquitously partitioned between 0.2 μm and 0.02 μm filtrations, indicating that the pore water distributions of Fe and Mn in the (traditionally termed) ‘dissolved’ size fraction are dominated by colloids, with respective mean abundances of 80% and 61%. Plausible mechanisms for the origin and composition of pore water colloids are discussed, and include prolonged exposure of Crozet surface sediments to early diagenesis compared to Montserrat, favouring nano-particulate goethite formation, and the elevated dissolved Si concentrations, which are shown to encourage fine-grained smectite formation. In addition, organic matter may stabilise authigenic Fe and Mn in the Crozet pore waters. We conclude that volcanogenic sediment diagenesis leads to a flux of colloidal material to the overlying bottom water, which may impact significantly on deep ocean biogeochemistry. Diffusive flux estimates from Montserrat suggest that diagenesis within tephra deposits of active island volcanism may also be an important source of dissolved Mn to the bottom waters, and therefore a source for the widespread hydrogenous MnO_x deposits found in the Caribbean region.     

Hydrological and geochemical control of metals and arsenic in a Mediterranean river contaminated by acid mine drainage (the Amous River,France); preliminary assessment of impacts on fish (Leuciscus cephalus)

Dissolved and particulate concentrations of metals (Fe, Al, Mn, Co, Ni, Cu, Zn, Cd, Tl, Pb) and As were monitored over a 5 year period in the Amous River downstream of its confluence with a creek severely affected by acid mine drainage (AMD) originating from a former Pb–Zn mine. Water pH ranged from 6.5 to 8.8. Metals were predominantly in dissolved form, except Fe and Pb, which were in particulate form. In the particulate phase, metals were generally associated with Al oxides, whereas As was linked to Fe oxides. Metal concentrations in the dissolved and/or particulate phase were generally higher during the wet season due to higher generation of AMD. Average dissolved (size < 0.22 μm) metal concentrations (μg/L) were 1 ± 4 (Fe), 69 ± 49 (Al), 140 ± 118 (Mn), 4 ± 3 Co, 6 ± 4 (Ni), 1.3 ± 0.8 (Cu), 126 ± 81 (Zn), 1.1 ± 0.7 (Cd), 0.9 ± 0.5 (Tl), 2 ± 3 (Pb). Dissolved As concentrations ranged from 5 to 134 μg/L (30 ± 23 μg/L). During the survey, the concentration of colloidal metals (5 kDa < size < 0.22 μm) was less than 25% of dissolved concentrations. Dissolved metal concentrations were generally higher than the maximum concentrations allowed in European surface waters for priority substances (Ni, Cd and Pb) and higher than the environmental quality standards for other compounds. Using Diffusion Gradient in Thin Film (DGT) probes, metals were shown to be in potentially bioavailable form. The concentrations in Leuciscus cephalus were below the maximum Pb and Cd concentrations allowed in fish muscle for human consumption by the European Water Directive. Amongst the elements studied, only As, Pb and Tl were shown to bioaccumulate in liver tissue (As, Pb) or otoliths (Tl). Bioaccumulation of metals or As was not detected in muscle.     

Fe–Al–organic Colloids Control of Trace Elements in Peat Soil Solutions: Results of Ultrafiltration and Dialysis

Size fractionation of ~40 major and trace elements (TE) in peat soil solutions from the Tverskaya region (Russia) has been studied using frontal filtration and ultrafiltration through a progressively decreasing pore size (5, 2.5, 0.22 μm, 100, 10, 5, and 1 kD) and in situ dialysis through 6–8 and 1 kD membranes with subsequent analysis by ICP-MS. In (ultra) filter-passed permeates and dialysates of soil solutions, Fe, Al, and organic carbon (OC) are well correlated, indicating the presence of mixed organo-mineral colloids. All major anions and silica are present in “dissolved” forms passed through 1 kD membrane. According to their behavior during filtration and dialysis and association with mineral or organic components, three groups of elements can be distinguished: (i) species that are weakly affected by size separation operations and largely (>50–80%) present in the form of dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, As, Mn) with some proportion of small (1–10 kD) organic complexes (Ca, Mg, Sr, Ba), (ii) biologically essential elements (Co, Ni, Zn, Cu, Cd) mainly present in the fraction smaller than 1 kD and known to form strong organic complexes with fulvic acids, and, (iii) elements strongly associated with aluminum, iron and OC in all ultrafiltrates and dialysates with 30–50% being concentrated in large (>10 kD) colloids (Ga, Y, REEs, Pb, Cd, V, Nb, Sn, Ti, Zr, Hf, Th, U). For most trace metals, the proportion in the colloidal fraction correlates with their first hydrolysis constant. This implies a strong control of negatively charged oxygen donors present in inorganic/organic colloids on TE distribution between aqueous solution and colloid particles. It is suggested that these colloids are formed during plant uptake of Al, Fe, and TE from mineral matrix of deep soil horizons and their subsequent release in surface horizons after litter degradation and oxygenation on redox or acid/base fronts. Dissolved organic matter stabilizes Al/Fe colloids and thus enhances trace elements transport in soil solutions.     

Metal speciation in rivers affected by enhanced soil erosion and acidity

Dissolved (<1 kDa), colloidal (1 kDa–0.45 μm) and particulate (>0.45 μm) size fractions of 30 elements were determined for four rivers (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), including 12 low-order inflow streams, largely affected by soil erosion and acidity in SW Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these rivers. Total metal concentrations were relatively high but most of the elements occurred mainly in a colloidal or particulate form and even elements expected to be very soluble occurred to a large extent in colloidal form. According to geochemical modelling these patterns could be explained by in-stream metal complexation/adsorption only to a limited extent. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of acid sulphate (AS) soils, known to exist in the catchment, could be clearly distinguished in Sirppujoki river as it had very high concentrations of dissolved metals, while in the two nearby rivers (Laajoki and Mynäjoki) the influence of AS soils was largely masked by eroded phyllosilicates. In Paimionjoki river the colloidal and particulate fractions dominated very strongly, indicating that total metal concentrations are almost solely controlled by erosion of phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high “background” metal concentrations due to erosion of relatively non-toxic colloidal/particulate phyllosilicates. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring and/or speciation modelling can lead to a great overestimation of the water toxicity in this environment.     

Association of dissolved radionuclides released by the Chernobyl accident with colloidal materials in surface water

The association of dissolved ⁹⁰Sr, ^239,240Pu and ²⁴¹Am with natural colloids was investigated in surface waters in the Chernobyl nuclear accident area. A 4-step ultrafiltration (UF) study (<1 kilodaltons (Da), 1–10 kDa, 10–100 kDa, 100 kDa<) showed that 49–83% of ^239,240Pu and 76% of ²⁴¹Am are distributed in colloids of the two size fractions larger than 10 kDa (nominal molecular weight limit of the filter, NMWL), while ⁹⁰Sr was found exclusively (85–88%) in the lowest molecular size fraction below 1 kDa (NMWL) for the Sahan River water at the highly contaminated area close to the Chernobyl Nuclear Power Plant (ChNPP). Consistent results were obtained by 2-step fractionation (larger than and smaller than 10 kDa (NMWL)) for river and lake waters including other locations within about 30 km away from ChNPP. It is likely that Pu and Am isotopes were preferentially associated with dissolved organic matter of high molecular size, as suggested by the fact that (i) only a few inorganic elements (Mg, Ca, Sr, Si, Mn, Al) were found in the colloidal size ranges, and (ii) the positive correlation between dissolved organic C (DOC) concentrations and UV absorbance at 280 nm, a broad absorption peak characteristic of humic substances (HS) was found. A model calculation on the complexation of Pu and Am with HS as an organic ligand suggests that the complexed form could be dominant at a low DOC concentration of 1 mgC L⁻¹, that is commonly encountered as a lower limit in fresh surface water. The present results suggest the general importance of natural organic colloids in dictating the chemical form of actinides in the surface aquatic environment.     

Size Fractionation of Trace Elements in a Seasonally Stratified Boreal Lake: Control of Organic Matter and Iron Colloids

The colloidal distribution and size fractionation of organic carbon and trace elements were studied in a seasonally stratified, organic-rich boreal lake, Lake Maselga, located in the European subarctic zone (NW Russia, Arkhangelsk region). This study took place over the course of 5?years in winter (glacial) and summer periods and during the spring and autumn overturn. A newly developed in situ dialysis technique (1, 10, and 50?kDa) and traditional frontal filtration and ultrafiltration (20, 10, 5, 0.22, and 0.025???m) were used to assess element concentrations at different depths. No significant changes in element concentrations occurred during filtration through sub-colloidal pore-size membranes (20?C0.22???m), suggesting a negligible amount of particulate Fe, OC, and associated trace metals. Large colloids (0.025?C0.22???m) were found to be the main carriers of poorly soluble elements (Fe, Al, Ti, Zr, REEs, Th, and U) during the summer and winter stratification. There was also a clear change in the vertical pattern of the percentage of colloidal Al, Ti, V, Cr, Fe, and Ni during different seasons, and the greatest proportion of colloidal forms was observed during the spring and autumn overturn. This pattern is most likely linked to the dominance of soil (allochthonous) organic carbon, which complexes with trace metals during these periods. During the summer seasons, autochthonous production of small exometabolites or photodegradation increases the concentration of the low-molecular weight fractions (<1?kDa) that dominate the speciation of divalent heavy metals in surface horizons. The colloidal status of As (30?C60%), which was documented in different seasons along the full depth of the water column, is most likely linked to the presence of organic complexes. The overall results of this study suggest that changes in the colloidal speciation of trace elements with depth in different seasons depend on changes in the redox conditions, the input of soil OM, the biodegradation of plankton biomass releasing dissolved organic matter in the bottom horizons, and in upward diffusion from the sediments.     

The influence of colloidal material on aluminium speciation and estimated acid neutralising capacity (ANC)

Cationic Al species (Al_i) cause toxic effects towards fish in acidified water. As several factors can influence the Al_i-speciation, acid neutralising capacity (ANC) has been applied as an alternative indicator for acidification and effects towards fish. However, the critical range of ANC for biological stress has been shown to be dependent upon the concentration of organic material (DOC). Using in situ size fractionation techniques the influence of particulate and colloidal DOC (0–400 μM) on Al_i-speciation and ANC-values was investigated in Norwegian streams. During high flow events with high river transport of DOC the Al_i concentration increased by a factor of 2 due to retention of colloidal Al species (>10 kDa), probably organic, in the chromatography column. Ultrafiltration (?10 kDa) of water prior to chromatography reduced the influence of non-toxic organic Al-species, on Al_i-speciation. The charge balanced ANC-values (ANC_cb) were also significantly lower (on average 34 μeq L⁻¹) in ultrafiltered water compared to unfiltered water samples, as base cations were associated with colloidal DOC (>10 kDa to 0.45 μm) and organic acids were not incorporated in the ANC_cb estimate. Thus, ANC_cb will underestimate the acidification effects towards fish in organic waters increasing with concentration of colloidal DOC present. Alkalinity based ANC-values (ANC_alk), which include a fraction of organic acids, were similar in unfiltered and ultrafiltered waters, but higher than ANC_cb-values of ultrafiltered samples. Thus, ANC_alk-values also underestimate the acidification effects on fish in organic waters. Based on ultrafiltered samples, however, ANC_cb-values was negatively correlated with Al_i independent of the DOC present and thus a more correct indicator for toxic Al-species.     

Changes in size distribution of fresh water nanoscale colloidal matter and associated elements on mixing with seawater

Changes in size distribution and elemental composition of 0.5-50 nm fresh water colloids during estuarine mixing have been studied by in-laboratory mixing of natural creek water and synthetic seawater, followed by size fractionation with Asymmetrical Flow Field-Flow Fractionation, and online elemental quantification by High-Resolution ICPMS. At least two types of colloids were present in the studied size region; 0.5-3 nm fluorescent dissolved organic matter (FDOM), and >3 nm colloids that were rich in Fe and colored dissolved organic matter (CDOM). Most trace elements were associated in different proportions to these two populations of colloids. Following mixing with synthetic seawater, the >3 nm Fe-rich colloids and CDOM were extensively removed from the studied size region by salt induced aggregation. The degree of removal with increasing salinity was greatest below 2.5‰ salinity, continued to a lesser degree between 2.5‰ and 15‰ salinity, above which only very small additional removal could be distinguished. At 25‰ salinity, the Fe concentration in the 0.5-50 size region had been reduced down to 15% of its original value in freshwater, while the amount of CDOM had been reduced to 55%. On the contrary, the concentration of the 0.5-3 nm FDOM was unchanged by the increased concentration of sea salt. Therefore, colloidally associated Al, P, Co, Cu, Zn, Ce, Lu and Pb were removed from the 0.5-50 nm size region according to their relative distributions between the FDOM and the Fe-rich colloids. Consequently, at 25‰ salinity, the 0.5-50 nm concentrations of Al, Mn, P and Pb, (mainly associated with the Fe-rich colloids) had been reduced down to 13-26 % of their values in freshwater, while the concentrations of Co and Cu (with higher preferences for FDOM) were less reduced, down to 46% and 57%, respectively. Changes in the elemental composition of the remaining colloidal matter were observed, the most pronounced were increased contents of P, Al and Pb in Fe-rich colloidal matter of medium size (∼3-15 nm) and increased Pb content in Fe-rich colloidal matter of larger size (∼5-50 nm).     

Formation of uranium(IV)-silica colloids at near-neutral pH

Evidence is provided by photon correlation spectroscopy, ultrafiltration and ultracentrifugation that uranium(IV) can form silicate-containing colloids of a size of ?20 nm. A concentration of up to 10⁻³ M of colloid-borne U(IV) was observed. The particles are generated in near-neutral to slightly alkaline solutions containing background chemicals of geogenic nature (carbonate, silicate, sodium ions). They remain stable in aqueous suspension over years. Electrostatic repulsion due to a negative zeta potential in the near-neutral to alkaline pH range caused by the silicate stabilizes the U(IV) colloids. The isoelectric point of the nanoparticles is shifted toward lower pH values by the silicate. The mechanism of the colloidal stabilization can be regarded as “sequestration” by silicate, a phenomenon well known from heavy metal ions of high ion potential such as iron(III) or manganese(III,IV), but never reported for uranium(IV) so far. Extended X-ray absorption fine structure (EXAFS) spectroscopy showed that U-O-Si bonds, which increasingly replace the U-O-U bonds of the amorphous uranium(IV) oxyhydroxide with increasing silicate concentrations, make up the internal structure of the colloids. The next-neighbor coordination of U(IV) in the U(IV)-silica colloids is comparable with that of coffinite, USiO₄. The assessment of uranium behavior in the aquatic environment should take the possible existence of U(IV)-silica colloids into consideration. Their occurrence might influence uranium migration in anoxic waters.     

Distribution of colloidal trace metals in the San Francisco Bay estuary

The size distribution of trace metals (Al, Ag, Cd, Cu, Fe, Mn, Ni, Sr, and Zn) was examined in surface waters of the San Francisco Bay estuary. Water samples were collected in January 1994 across the whole salinity gradient and fractionated into total dissolved (<0.2 μm colloidal (10 KDa–0.2 μm) and < 10 kDa molecular weight phases. In the low salinity region of the estuary, concentrations of colloidal A1, Ag, and Fe accounted for ≥84% of the total dissolved fraction, and colloidal Cu and Mn accounted for 16–20% of the total. At high salinities, while colloidal Fe was still relatively high (40% of the dissolved), very little colloidal Al, Mn, and Cu (<10%) and no colloidal Ag was detectable. Colloidal Zn accounted for <3% of the total dissolved along the estuary, and colloidal Ni was only detectable (<2%) at the river endmember. All of the total dissolved Cd and Sr throughout the estuary consisted of relatively low molecular weight (<10 kDa) species. The relative affinity of metals for humic substances and their reactivity with particle surfaces appear to determine the amounts of metal associated with colloids. The mixing behavior of metals along the estuary appears to be determined by the relative contribution of the colloidal phase to the total dissolved pool. Metals with a small or undetectable colloidal fraction showed a nonconservative excess (Cd, Cu, Ni, and Mn) or conservative mixing (Sr) in the total dissolved fraction, relative to ideal dilution of river water and seawater along the estuary.

The salt-induced coagulation of colloidal A1, Fe, and Cu is indicated by their highly nonconservative removal along the salinity gradient. However, colloidal metals with low affinity for humic substances (Mn and Zn) showed conservative mixing behavior, indicating that some riverine colloids are not effectively aggregated during their transport to the sea. While colloidal metal concentrations correlated with dissolved organic carbon, they also covaried with colloidal Al, suggesting that colloids are a mixture of organic and inorganic components. Furthermore, the similarity between the colloidal metal:A1 ratios with the crustal ratios indicated that colloids could be the product of weathering processes or particle resuspension. Distribution coefficients for colloidal particles (K_c) and for large, filter-retained particles (K_d) were of the same magnitude, suggesting similar binding strength for the two types of particles. Also, the dependence of the distribution coefficients on the amount of suspended particulate matter (the so-called particle concentration effect) was still evident for the colloids-corrected distribution coefficient (K_p+c) and for metals (e.g., Ni) without affinity for colloidal particles.     

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes

Seasonal (Spring and Summer 2002) concentrations of dissolved (<0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO₃, PO₄, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO₄ and NO₃ (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 10²– 8.2 × 10³ μmol d⁻¹). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 10³ μmol d⁻¹ (inland, freshwater well) vs. 2.1 × 10⁵ μmol d⁻¹(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.     

Temporal variations of colloidal carrier phases and associated trace elements in a boreal river

Elemental size distributions, from truly dissolved through colloidal to particulate, have been studied in a subarctic boreal river. The measurements, carried out during 2002, ranged from winter to summer conditions, including an intense spring flood event. Results are reported for a total of 42 elements. Size distributions were characterised using a combination of cross-flow (ultra)filtration (CFF), flow field-flow fractionation (FlFFF), and diffusive gradients in thin-films (DGT). The three techniques showed similar trends, but quantitative comparisons reveal some important differences that warrant further investigation.Previous work has identified two colloidal carrier phases in fresh waters, dominated by iron and carbon, respectively. The majority of the elements studied are associated with one or both of these colloidal carrier phases. The exceptions are the alkali metals and several anions that are only very weakly associated with colloidal material, and which therefore occur mainly as truly dissolved material (<1 kDa in molecular weight). We discuss the likely origin for the two colloidal carrier phases and consider how associated trace elements fit into the geochemical framework. The relative affinities of the elements for iron and carbon colloidal carrier phases are related to their chemistries, and are compared with earlier data from the Delsjö Creek in southern Sweden.Elemental colloidal concentrations show strong seasonal variations related to changes in the colloidal carrier phase(s) with which they associate. In particular, many elements show a strong spring maximum in colloidal concentrations associated with the strong maximum in colloidal carbon concentration during the spring flood.     

The effects of the San Francisco Bay plume on trace metal and nutrient distributions in the Gulf of the Farallones

The distributions of particulate elements (Al, P, Mn, Fe, Co, Cu, Zn, Cd, and Pb), dissolved trace metals (Mn, Fe, Co, Cu, Zn, and Cd), and dissolved nutrients (nitrate, phosphate, and silicic acid) were investigated in the Gulf of the Farallones, a region of high productivity that is driven by the dynamic mixing of the San Francisco Bay plume, upwelled waters, and California coastal surface waters. Particulate metals were separated into >10 and 0.4-10 μm size-fractions and further fractionated into leachable (operationally defined with a 25% acetic acid leach) and refractory particulate concentrations. Dissolved metals (< 0.4 μm pore-size filtrate) were separated into colloidal (0.03-0.4 μm) and soluble (<0.03 μm) fractions. The percent leachable particulate fractions ranged from 2% to 99% of the total particulate concentration for these metals with Mn and Cd being predominantly leachable and Fe and Al being predominantly refractory. The leachable particulate Pb concentration was associated primarily with suspended sediments from San Francisco Bay and was a tracer of the plume in coastal waters. The particulate trace metal data suggest that the leachable fraction was an available source of trace metal micronutrients to the primary productivity in coastal waters. The dissolved trace metals in the San Francisco Bay plume and freshly upwelled surface waters were similar in concentration, with the exception of Cu and Co, which exhibited relatively high concentrations in plume waters and served as tracers of this water mass. The dissolved data and estimates of the plume dynamics suggest that the impact of anthropogenic inputs of nutrients and trace metals in the San Francisco Bay plume contributes substantially to the concentrations found in the Gulf of the Farallones (10-50% of estimated upwelled flux values), but does not greatly disrupt the natural stoichiometric balance of trace metal and nutrient elements within coastal waters given the similarity in concentrations to sources in upwelled water. In all, the data from this study demonstrate that the flux of dissolved nutrients and bioactive trace metals from the San Francisco Bay plume contribute to the high and relatively constant phytoplankton biomass observed in the Gulf of the Farallones.